Compositions and processes for printing organic derivatives of cellulose using a mixture of four swelling agents



Patented Nov. 13, 951

OFFICE COMPOSITIONS AND PROCESSES ,EOR

PRINTING ORGANIC DERIVATIVES OF 1 CELLULOSE' "USING A MIXTURE OF FOUR SWELIJING AGENTS Alexis'Wiazmitinow" and Henk Goorhuis, Basel, Switzerlanmassignors to Sandoz A. G., Basel,

Switzerland, a: Swiss firm; I

No Drawing; Application May 9, 1949, Serial No.

92,246. In Switzerland 14, 1948 p The present invention relatesto anew and improved process for the dyeing and printinggwof organic derivatives;- of cellulose; allowing dyestuffs of various constitution to be fixed on the saidcellulose derivatives without use of: asteaming operation. Untilnow different processes for the fixation of water-soluble aciddyestuffs onicellulose esters and ethers have been suggested. In. order to obtain this result it has been proposedzto add to the dyebaths or printing pastes compounds, such as aliphatic carboxylic acids or alicohols, esters of organic acids, such as. ethyl. acetate, acetine and the like, and furthermore; swelling agentasuch as the salts of: thiocyanic" acid, phenols andthe like. Generally'the'fixation. of the dyestuffs is realized by subjecting vthe" printed material to a steaming operation; 'Itisl' further known that by the useof an increased" quantity of sodium thiocyanate in the presence of methanol and acetic acid, aciddyestufis may be printed on acetatesilk and fixed by, a simple drying of the printed material. Butthisfixation'; is not a quantitative one and the strong swelling action of the sodium thiocyanate can easily provoke a destruction of thefibre and-of the-acid azo dyestuff which becomes reduced by the-sodium thiocyanate.

It has now been found'that organic derivatives of cellulose can be dyed or. printed in shades fast to washing by means of. water-soluble dyestuffs which have no or apoor affinity: to such? cellulose derivatives, when during the dyeing or printingof. such fibres padding baths or printingvpaste sxare used which contain besides the said dyestuffs and conventional stretching and diluting agents at least one water-soluble salt of thiocyanic acid, a swelling agent of the generalformula wherein X stands for O, S or NH, a volatileali phatic carboxylic acid and an aliphatie liydroxylated compound. The quantity of the salt of the thiocyanic acid which is used according: to the present invention maybe for instance about 3% in the case of sodium, thiocya'n'ate; calculated on the weight of the dye-bathor printing paste.

As swelling. agents falling within the 'scop'eof the above general formula, u'sefmay be made of urea, thiourea and guanidine. Q a

As volatile aliphatic carboxylic" acids? we; use preferably formic andacetic acid and'as aliphatic hydroxylated compounds glycols, polyglycols be employedi group, thiodig'lycolsfaiid similar compounds may The fixation of the dyes is realized by a simple drying of the dyed or printed material ata tem perature of for examplev40-50 C. After drying,

the material is preferably first washed with cold Water;- then soaped;: at.- G. and finished in the conventional manner.

The present invention is-particularly suitable for. printing and dyeing, bypadding acetate silk. If it. is applied tomixed fabrics containing for example. acetate' andspuresilk it is advisable to have a steam operation to follow theyprinting or padding operation in order to=effect the fixation on both fibresthat-:istosay onthe cellulose acetate and also; the-si1k= fibre.

Thefollowing examples, without being limita-.

tive, show how the present inVentiOnTcan-be'car ried out.

EXAMPLE 1 A wpieceof acetate silk ispadded in'a bath of the following composition:

7.5 grams of acid Vio1et-4BNS (Colour Index grams, oft water;

grams of tragacanth thickening 60/1000 grams of ethylene glycol HO- --CH2.-CH2--OH" 7 grams of thiourea grams of ammonium thiocyanate grams of acetic acid com.

1000.0 grams 100.0 grams'ofureal 30.0 grams of. thiocyanate 7 100.0 grams of acetic acid com. 100% their ethers containing at least one fi'sehyaroxy 1000.0 grams 15.0 grams of Azo Rhodine 2G (Colour Index -40). I 7 155.0 grams of water 500.0 grams of tragacanth thickening 60/1000 100.0 grams of ethylene thiodiglycol 100.0 grams of thiourea 30.0 grams of ammonium thiocyanate 100.0 grams of formic acid 80% 1000.0 grams 25.0 grams of Brilliant sulpnbn Red is (colour Index 41) 145.0 grams of water 500.0 grams of tragacanth thickening'60/1000' 100.0 grams of ethylene thiodiglycol 100.0 grams of thiourea l;

30.0 grams of ammoniumthiocyanate 100.0 grams of acetic acid conc. 100%,

1000.0 grams 15.0 grams of Xylene Light Yellow R (Colour Index736) 145.0 grams of water 1 500.0 grams of tragacanth thickening -60/ 1000 100.0 grams of ethylene thiodiglycol 100.0 grams of thiourea 40.0 grams of zinc thiocyanate 100.0 grams of acetic acid conc. 100% 1000.0 grams 7.5 grams of Xylene Red B (Colour Index 863) 152.5 grams of water 500.0 grams of tragacanth thickening 60/1000 100.0 grams of ethylene thiodiglycol 100.0 grams of thiourea 40.0 grams of potassium thiocyanate" 100.0 grams of acetic acid conc. 100% 1000.0 grams H I 15.0 grams of Xylene Blue AS (Colour Index 140.0 grams of water 500.0 grams of tragacanth thickening60/ 1000 100.0 grams of thiourea I v 100.0 grams of ethylene thiodiglycol 45.0 grams of barium thiocyanate 2 aq. 100.0 grams of acetic acid conc. 100% 1000.0 grams grams of Xylene Red B (Colour Index 863) grams of water grams of tragacanth thickening 60/ 1000 grams of ethylene thiodiglycol grams of thiourea grams of potassium thiocyanate grams of sodium thiocyanate grams of acetic acid conc.

1000.0 grams The printed material is dried at 40-50 C., rinsedwith cold water and soaped at 60 C. The material printed in this way may be soaped at boiling temperature without bleeding.

I EXAMPLE 3 A printing paste containing 12.0 grams of Alizarine Light Green GS (Colour Index 1201) grams of water grams of tragacanth thickening 60/1000 grams of ethylene thiodiglycol grams of thiourea grams of ammonium thiocyanate grams of acetic acid com. 100

1000.0 grams is printed on a mixed fabric containing acetate silk and natural silk, whereupon .the printed piece is dried at a temperature of 40-50" C., steamed for 5' minutes at 101 C., rinsed with cold water and soaped at 60 C. The print obtained in this way is fast to washing, the acetate silk fibres having not been damaged by the swelling agent present in the printing paste.

EXAMPLE 4 Acetate silk is printed with any one of the following printing pastes of the following composition:

10.0 grams of Auramine 0 (Colour Index 655) 100.0 grams of ethylene thiodiglycol 160.0 cc. of water 500.0 grams of tragacanth thickening 6071000 100.0 grams of thiourea I 30.0 grams of ammonium thiocyanate 100.0 grams of acetic acid conc. 100% 1000.0 grams 5.0 grams of Rhodamine B (Colour Index 749) 100.0 grams of ethylene glycol 165.0 cc. of water 500.0 grams of tragacanth thickening 60/ 1000 100.0 grams of thiourea 30.0 grams of ammonium thiocyanate 100.0 grams of acetic acid conc. 100

1000.0 grams 15.0 grams of Chlorantlne Light Yellow 4GL (Colour Index No. 346) 100.0 grams of ethylene thiodiglycol 155.0 cc. of water 500.0 grams of tragacanth thickening 60/1000 100.0 grams of thiourea I 30.0 grams of ammonium thiocyanate 100.0 grams of acetic acid cpnc. 100% 1000.0 grams The printed materials are dried at a temperature of 40-50 C., rinsed with cold water and soaped at 60 C., whereupon the material are once more rinsed. The prints obtained in this mannerare fast to soaping.

What we claim is:

1. A process for producing prints, which are fast to soaping, on textile materials composed of cellulose acetate, with a water-soluble dyestufi having substantially no affinity for cellulose acetate, which comprises the steps of applying to the said material an aqueous printing composition containing the said dyestuff, a thickening agent, 2-5% by weight of at least one watersoluble salt of thiocyanic acid, 23-12% by weight of a lower aliphatic carboxylic acid, 812% by weight of a swelling agent selected from the group consisting of urea, thiourea and guanidine, and 9-15% by weight of a member selected from the group consisting of ethylene glycol, ethylene thiodiglycol and diethylene glycol monobutyl ether, fixing the dye onto the thus-treated material by subjecting the latter to a simple heating operation, whereby the material is dried and the dye fixed thereon without the necessity of steaming, and then subjecting the dried material to a treatment with a warm soaping solution.

2. A process for producing prints, which are fast to soaping, on textile material composed of cellulose acetate, with a water-soluble acid dyestuff having substantially no affinity for cellulose acetate, which comprises the steps of applying tothe said material an aqueous printing composition containing the said dyestufi, a thickening agent, 2-5% by weight of at least one watersoluble salt of thiocyanic acid, 8-12% by weight of a lower aliphatic carboxylic acid, 842% by weight of a swelling agent selected from the group consisting of urea, thiourea and guanidine, and 59-15% by weight of a member selected from the group consisting of ethylene glycol, ethylene thiodiglycol and diethylene glycol monobutyl ether, fixing the dye onto the thus-treated material by subjecting the latter to a simple heating operation, whereby the material is dried and the dye fixed thereon without the necessity of steaming, and then subjecting the dried material to a treatment with a warm soaping solution.

3. A process for producing prints, which are fast to soaping, on textile material composed of cellulose acetate, with a water-soluble basic dyestufi having substantially no affinity for cellulose acetate, which comprises the steps of applying to the said material an aqueou printing composition containing the said dyestuff, a thickening agent, 2-5% by weight of at least one Watersoluble salt of thiocyanic acid, 8-12% by weight of a lower aliphatic carboxylic acid, 8-12% by weight of a swelling agent selected from the group consisting of urea, thiourea and guanidine, and 9-15% by weight of a member selected from the group consisting of ethylene glycol, ethylene 6 thiodiglycol and diethylene glycol monobutyl ether, fixing the dye onto the thus-treated material by subjecting the latter to a simple heating operation, whereby the material is dried and the dye fixed thereon without the necessity of steaming, and then subjecting the dried material to a treatment with a warm soaping solution. 4. A process for producing prints, which are 7 fast to soaping, on textile material composed of cellulose acetate, with a water-soluble substantive dyestufi having substantially no ailinity for cellulose acetate, which comprises the steps of applying to the said material an aqueous printing composition containing the said dyestufi, a thickening agent, 2-5% by weight of at least one water-soluble salt of thiocyanic acid, 8-12% by weight of a lower aliphatic carboxylic acid, 812% by weight of a swelling agent selected from thegroup' consisting of urea, thiourea and guanidine, and 9-15% by weight of a member selected from; the group consisting of ethylene glycol, ethylene thiodiglycol and diethylene glycol monobutyl ether, fixing the dye onto the thus-treated material .by subjecting the latter to a simple heat ing operation, whereby the material i dried and the dye fixed thereon without the necessity of steaming, and then subjecting the dried material to a treatment with a warm soaping solution.

5. A process for producing prints, which are fast to soaping, on textile material composed of cellulose acetate, with a water-soluble mordant dyestuif having substantially no aflmity for cellulose acetate, which comprises the steps of applying to the said material an aqueous printing composition containing the said dyestuif, a thickening agent, 2-5% by weight of at least one watersoluble salt of thiocyanic acid, 55-12% by weight of a lower aliphatic carboxylic acid, 8-12% by weight of a swelling agent selected from the group consisting of urea, thiourea and guanidine, and 9-15% by 'weight'of a member selected from the group consisting of ethylene glycol, ethylene thiodiglycol and diethylene glycol monobutyl ether, fixing the dye onto the thus-treated material by subjecting the latter to a simple heating operation, whereby the material i dried and the dye fixed thereon without the necessity of steaming, and then subjecting the dried material to a treatment with a warm soaping solution.

6. A textile printing composition for the production of prints, which are fast to soaping, on textile material composed of cellulose acetate, said composition consisting essentially of water, a water-soluble dyestuff having substantially no afiinity for cellulose acetate, a thickening agent, 2-5% by weight of at least one Water-soluble salt of thiocyanic acid, 812% by weight of a lower aliphatic carboxylic acid, 8-12% by Weight of a swelling agent selected from the group consisting of urea, thiourea and guanidine, and 915% by weight of a member selected from the group consisting of ethylene glycol, ethylene thiodiglycol and diethylene glycol monobutyl ether, whereby the desired prints which are fast to soaping may be produced without the necessity of subjecting the printed material to a steaming operation.

'7. A textile printing composition for the production of prints, which are fast to soaping, on textile material composed of cellulose acetate, said composition consisting essentially of Water, a water-soluble acid dyestufi having substantially no affinity for cellulose acetate, a thickening agent, 2-5% by weight of at least one water soluble salt of thiocyanic acid, 8-12% by weight of a lower aliphatic carboxylic acid, 23-12% by weight of a swelling agent selected from the group consisting of urea, thiourea and guanidine, and 91 by weight of a member selected from the groupconsisting of ethylene glycol, ethylene thiodiglycol and diethylene glycol monobutyl ether, whereby the desired prints which are fast to soapingmay be produced without the necessity of subjecting the printed material to a steam ing operation.

8. A textile printing composition for the production Of prints, which are fast to soaping,.on textile material composed of cellulose acetate, said composition consisting essentially of water, a water-soluble basic dyestufi having substantially no aiiinity for cellulose acetate, a thickening agent, 2-5% by weight of at least one Watersoluble salt of thiocyanic acid, 8-12% by weight of a lower aliphatic carboxylic acid, 8-12% by weight of a swelling agent selected from the group consisting of urea, thiourea and guanidine, and 945% by weight of a member selected from the group consisting of ethylene glycol, ethylene thiodiglycol and diethylene glycol monobutyl ether, whereby the desired prints which are fast to soaping may be produced without the necessity awgsoe to soaping may be produced without the necessity of subjecting the printed material to a steaming operation.

10. A textile printing composition for the production of prints, which are fast to soaping, on textile material composed of cellulose acetate,

said composition consisting essentially of water,

a water-soluble mordant dyestuff having substantially no afiinity for cellulose acetate, a thickening agent, 2-5% by weight of at least one watersoluble salt of thiocyanic acid, 8-12% by weight of subjecting the printed material to a steaming operation.

9. A textile printing composition for the production of prints, which are fast to soaping, on textile material composed of cellulose acetate, said composition consisting essentially of water, a water-soluble substantive dyestufi having substantially no aflinity for cellulose acetate, a thickening agent, 2-5% by weight of at least one water-soluble salt of thiocyanic acid, 8-12% by weight of a lower aliphatic carboxylic acid, 8-12% by weight of a swelling agent selected from the group consisting of urea, thiourea and guanidine, and 9-15% by Weight of a member selected from the group consisting of ethylene glycol, ethylene thiodiglycol and diethylene glycol monobutyl ether, whereby the desired prints which are fast of a lower aliphatic carboxylic acid, 8-12% by weight of a swelling agent selected from the group consisting of urea, thiourea and guam'dine, and 9-15% by weight of a member selected from the group consisting of ethylene glycol, ethylene thiodiglycol and diethylene glycol monobutyl ether, whereby the desired prints which are fast to soaping may be produced without the necessity of subjecting the printed material to a steaming operation.

ALEXIS WIAZMITINOW.

HENK GOORHUIS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,968,855 Rivat Aug. 7, 1934 2,428,836 Croft Oct. 14, 1947 FOREIGN PATENTS Number Country Date 285,942 Great Britain Feb. 23, 1928 595,344 Great Britain Dec. 2, 1947 376,797 Great Britain June 11, 1932 375,313 Great Britain June 13, 1932 OTHER REFERENCES Rayon Textile M0. for March 1948, page 90. 

1. A PROCESS FOR PRODUCING PRINTS, WHICH ARE FAST TO SOAPING, ON TEXTILE MATERIALS COMPOSED OF CELLULOSE ACETATE, WITH A WATER-SOLUBLE DYESTUFF HAVING SUBSTANTIALLY NO AFFINITY FOR CELLULOSE ACETATE, WHICH COMPRISES THE STEPS OF APPLYING TO THE SAID MATERIAL AN AQUEOUS PRINTING COMPOSITION CONTAINING THE SAID DYESTUFF, A THICKENING AGENT, 2-5% BY WEIGHT OF AT LEAST ONE WATERSOLUBLE SALT OF THIOCYANIC ACID, 8-12% BY WEIGHT OF A LOWER ALIPHATIC CARBOXYLIC ACID, 8-12% BY WEIGHT OF A SWELLING AGENT SELECTED FROM THE GROUP CONSISTING OF UREA, THIOUREA AND GUANIDINE, AND 9-15% BY WEIGHT OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF UREA, THIOUREA AND GUANIDINE THIODIGLYCOL AND DIETHYLENE GLYCOL MONOBUTYL ETHER, FIXING THE DYE ONTO THE THUS-TREATED MATERIAL BY SUBJECTING THE LATTER TO A SIMPLE HEATING OPERATION, WHEREBY THE MATERIAL IS DRIED AND THE DYE FIXED THEREON WITHOUT THE NECESSITY OF STEAMING, AND THEN SUBJECTING THE DRIED MATERIAL TO A TREATMENT WITH A WARM SOAPING SOLUTION. 